Compositions comprising metathesized unsaturated polyol esters

ABSTRACT

Disclosed are petrolatum-like compositions that include metathesized unsaturated polyol esters. Also disclosed are emulsions that include metathesized unsaturated polyol esters. The petrolatum-like compositions may be used as substitutes for petroleum-based petrolatum. The emulsions may be water-in-oil or oil-in-water emulsions and may be suitable for a variety of end uses.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 12/281,938, whichwas filed on Dec. 11, 2008, which claims the benefit under 35 U.S.C.§371 of International Application No. PCT/US2007/005736, filed Mar. 7,2007, which claims the benefit of U.S. Provisional Application Ser. No.60/780,125, filed Mar. 7, 2006, the disclosures of which areincorporated herein by reference.

BACKGROUND

Petroleum-based petrolatum and wax compositions are well known and arecommonly used in a variety of applications including, for example,creams, lotions, hair preparations, cosmetics, candles, ointments,lubricants, adhesives, and coatings. In view of the non-renewable natureof petroleum, it is highly desirable to provide non-petroleumalternatives for materials, such as petrolatums or waxes that havehistorically been produced from petroleum.

SUMMARY

In one aspect the invention provides petrolatum-like compositions ofmatter comprising metathesized unsaturated polyol esters. In manyembodiments, the petrolatum-like compositions of the invention areviscous semi-solids at room temperature and, in many embodiments,display properties that are similar to petroleum-derived petrolatumcompositions, for example, cone penetration (ASTM D-937), congealingpoint (ASTM D-938), drop melt point (ASTM D-127), and viscosity (ASTMD-445/D-2161).

In some embodiments, petrolatum-like compositions of the inventioncomprise a hydrogenated (i.e., including fully and partiallyhydrogenated) metathesized unsaturated polyol ester that itself displaysthe desired petrolatum-like properties and that can be used by itself(or with the addition of other minor ingredients) as a petrolatum-likematerial. Accordingly, in some embodiments, the petrolatum-likecompositions consist essentially of or consist of a hydrogenatedmetathesized unsaturated polyol ester. Typically, the degree ofhydrogenation (e.g., as measured by iodine value (IV)) and the extent ofoligomerization of the metathesized polyol ester are controlled toprovide a hydrogenated metathesized unsaturated polyol ester havingpetrolatum-like properties.

In some embodiments, the petrolatum-like compositions of the inventioncomprise a mixture of: (a) a metathesized unsaturated polyol ester; and(b) a polyol ester. In some embodiments, the metathesized unsaturatedpolyol ester is hydrogenated. The properties of the petrolatum-likecomposition may be controlled, for example, by varying one or more ofthe following: (a) the degree of hydrogenation of the metathesizedunsaturated polyol ester, (b) the degree of oligomerization of themetathesized unsaturated polyol ester, (c) the degree of hydrogenationof the polyol ester, and/or (d) the relative amounts of components (i)and (ii) in the composition.

In some embodiments, the metathesized unsaturated polyol ester is ametathesized vegetable oil, for example, metathesized soybean oil,metathesized canola oil, methathesized rapeseed oil, metathesizedcoconut oil, metathesized corn oil, metathesized cottonseed oil,metathesized olive oil, metathesized palm oil, metathesized peanut oil,metathesized safflower oil, metathesized sesame oil, metathesizedsunflower oil, metathesized linseed oil, metathesized palm kernel oil,metathesized tung oil, and metathesized castor oil. In otherembodiments, the metathesized unsaturated polyol ester is a metathesizedanimal fat, for example, metathesized lard, metathesized tallow,metathesized chicken fat (i.e., yellow grease), and metathesized fishoil. Mixtures of the foregoing may also be useful.

In exemplary embodiments, the metathesized unsaturated polyol ester ishydrogenated (i.e., including fully and partially hydrogenated).Representative examples include hydrogenated metathesized vegetable oil,for example, hydrogenated metathesized soybean oil, hydrogenatedmetathesized canola oil, hydrogenated metathesized rapeseed oil,hydrogenated metathesized coconut oil, hydrogenated metathesized cornoil, hydrogenated metathesized cottonseed oil, hydrogenated metathesizedolive oil, hydrogenated metathesized palm oil, hydrogenated metathesizedpeanut oil, hydrogenated metathesized safflower oil, hydrogenatedmetathesized sesame oil, hydrogenated metathesized sunflower oil,hydrogenated metathesized linseed oil, hydrogenated metathesized palmkernel oil, hydrogenated metathesized tung oil, hydrogenatedmetathesized castor oil, hydrogenated metathesized lard, hydrogenatedmetathesized tallow, hydrogenated metathesized chicken fat (yellowgrease), and hydrogenated metathesized fish oil. Mixtures of theforegoing may also be useful.

In many embodiments, the metathesized unsaturated polyol ester orhydrogenated metathesized unsaturated polyol ester comprises one or moreof metathesis monomers, metathesis dimers, metathesis trimers,metathesis tetramers, metathesis pentamers, and higher order metathesisoligomers. Typically, the metathesized unsaturated polyol ester orhydrogenated metathesized unsaturated polyol ester comprises a mixtureof metathesis monomers, metathesis dimers, metathesis trimers,metathesis tetramers, metathesis pentamers, and higher order metathesisoligomers.

In many embodiments, the polyol ester component of the petrolatum-likecomposition comprises a natural oil, such as a vegetable oil, algae oil,or an animal fat. Examples of vegetable oils include canola oil,rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palmoil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil,linseed oil, palm kernel oil, tung oil, castor oil, and the like.Mixtures may also be useful. The vegetable oil may be partiallyhydrogenated, winterized, or partially hydrogenated and winterized. Inan exemplary embodiment, the vegetable oil is refined, bleached, anddeodorized (RBD) soybean oil.

In many embodiments, the metathesized unsaturated polyol ester orhydrogenated metathesized unsaturated polyol ester is present in thepetrolatum-like composition in an amount of about 50% wt. or less, forexample, about 40% wt. or less, about 30% weight or less, about 25% wt.or less, about 20% wt. or less, about 15% wt. or less, or about 10% wt.or less. In an exemplary embodiment, the petrolatum-like compositioncomprises about 30% wt. or less hydrogenated metathesized soybean oil,and about 70% wt. or greater refined, bleached, and deodorized (i.e.,RBD) soybean oil. In another exemplary embodiment, the petrolatum-likecomposition comprises about 5% wt. to about 25% wt. hydrogenatedmetathesized soybean oil, and about 75% wt. to about 95% wt. soybeanoil.

In some embodiments, the petrolatum-like compositions of the inventionhave a cone penetration @ 77° F. (25° C.) (ASTM D-937) that is similarto petroleum-derived petrolatum. For example, in some embodiments, thecompositions have a cone penetration @ 77° F. (25° C.) of about 100 dmmto about 300 dmm. In exemplary embodiments, the compositions have a conepenetration @ 77° F. (25° C.) of about 150 dmm to about 160 dmm.

In some embodiments, the petrolatum-like compositions of the inventionhave a congealing point (ASTM D938) that is similar to petroleum-derivedpetrolatum. For example, in some embodiments the compositions have acongealing point of about 100° F. to about 140° F. (37.8° C. to 60° C.).In exemplary embodiments, the compositions have a congealing point ofabout 105° F. to about 135° F. (40.6° C. to 57.2° C.).

In some embodiments, the petrolatum-like compositions of the inventionhave a drop melt point (ASTM D-127) that is similar to petroleum-derivedpetrolatum. For example, in some embodiments the compositions have adrop melt point of about 100° F. to about 150° F. (37.8° C. to 65.6°C.).

In some embodiments, the petrolatum-like compositions of the inventionhave a viscosity at 210° F. (ASTM D-445 and D-2161) that is similar tothat of petroleum-derived petrolatum. For example, in some embodimentsthe compositions have a kinematic viscosity of 100 SUS or less, moretypically about 40 SUS to about 90 SUS, or about 55 to about 80 SUS.

Petrolatum-like compositions of the invention may be used, for example,as substitutes for petroleum-derived petrolatum compositions.Representative examples of typical applications include personal careitems (e.g., cosmetics, lip balm, lipstick, hand cleaners, hairdressings, ointments, sun care products, moisturizers, pharmaceuticalointments, fragrance sticks, and perfume carriers); plastics (e.g., aprocessing aid for PVC); food (e.g., cheese coatings, baking grease);telecommunications (e.g., cable filling or flooding compounds);industrial applications (e.g., grain dust suppressant, rust preventativecoatings, adhesives, toilet boil rings, bone guard, and textilecoatings).

In another aspect, the invention provides emulsions comprisingmetathesized unsaturated polyol esters. The metathesized unsaturatedpolyol ester may be hydrogenated, for example, fully or partiallyhydrogenated. The emulsions may be oil-in-water emulsions orwater-in-oil emulsions. The oil phase of the emulsion may havepetrolatum-like properties or may be a metathesized wax. In someembodiments, the oil-in-water emulsions comprise: (a) a dispersed phasecomprising a metathesized unsaturated polyol ester, and (b) a continuousphase comprising water. In other embodiments, the oil-in-water emulsionscomprise: (a) a dispersed phase comprising a mixture of (i) ametathesized unsaturated polyol ester, and (ii) a polyol ester; and (b)a continuous phase comprising water.

Emulsions of the invention may be used, for example, as replacements forpetroleum-derived wax emulsions. Representative examples of applicationsfor the emulsions of the invention include in building materials (e.g.,coatings for oriented strand board (OSB) or medium density fiberboard,lumber coatings); metal coatings (e.g., slip coating for cans, coilcoatings); corrugated paperboard coatings; inks (e.g., additive toimprove rub or scuff resistance in water based inks); fiberglass (e.g.,antiblock or lubricant); molded latex articles (e.g., mold release forgloves or condoms); textiles (e.g., sizing agent or thread lubricant);floor finish (e.g., additive to impart rub resistance); flexible films(e.g., processing aid); coatings (e.g., to add water repellency to deckstains or wood varnishes); and fruit/vegetable coating (e.g., as amoisture barrier coating); cosmetic and personal care formulations(e.g., face, hand and body lotions/creams, lip care products, hair careproducts as a moisturizer or moisture barrier coating).

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described further in connection with the attacheddrawings, wherein like reference numbers have been used to indicate likeparts and wherein:

FIG. 1 is an exemplary metathesis reaction scheme.

FIG. 1A is an exemplary metathesis reaction scheme.

FIG. 1B is an exemplary metathesis reaction scheme.

FIG. 1C displays certain internal and cyclic olefins that may be byproducts of the metathesis reactions of FIGS. 1-1B.

FIG. 2 is a figure showing exemplary ruthenium-based metathesiscatalysts.

FIG. 3 is a figure showing exemplary ruthenium-based metathesiscatalysts.

FIG. 4 is a figure showing exemplary ruthenium-based metathesiscatalysts.

FIG. 5 is a figure showing exemplary ruthenium-based metathesiscatalysts.

FIG. 6 is a figure showing exemplary ruthenium-based metathesiscatalysts.

DETAILED DESCRIPTION

Metathesized Unsaturated Polyol Ester:

The petrolatum-like compositions and the emulsions of the inventioncomprise a metathesized unsaturated polyol ester. In some embodimentsthe metathesized unsaturated polyol esters is hydrogenated, for example,partially or fully hydrogenated.

A metathesized unsaturated polyol ester refers to the product obtainedwhen one or more unsaturated polyol ester ingredient(s) are subjected toa metathesis reaction. Metathesis is a catalytic reaction that involvesthe interchange of alkylidene units among compounds containing one ormore double bonds (i.e., olefinic compounds) via the formation andcleavage of the carbon-carbon double bonds. Metathesis may occur betweentwo of the same molecules (often referred to as self-metathesis) and/orit may occur between two different molecules (often referred to ascross-metathesis). Self-metathesis may be represented schematically asshown in Equation I.

R¹—CH═CH—R²+R¹—CH═CH—R²⇄R¹—CH═CH—R¹+R²—CH═CH—R²   (I)

-   -   where R¹ and R² are organic groups.

Cross-metathesis may be represented schematically as shown in EquationII.

R¹—CH═CH—R²+R³—CH═CH—R⁴⇄R¹—CH═CH—R³+R¹—CH═CH—R⁴+R²—CH═CH—R³+R²—CH═CH—R⁴+R¹—CH═CH—R¹+R²—CH═CH—R²+R³—CH═CH—R³+R⁴—CH═CH—R⁴  (II)

where R¹, R², R³, and R⁴ are organic groups.

When the unsaturated polyol ester comprises molecules that have morethan one carbon-carbon double bond (i.e., a polyunsaturated polyolester), self-metathesis results in oligomerization of the unsaturatedpolyol ester. The self-metathesis reaction results in the formation ofmetathesis dimers, metathesis trimers, and metathesis tetramers. Higherorder metathesis oligomers, such as metathesis pentamers and metathesishexamers, may also be formed by continued self-metathesis.

As a starting material, metathesized unsaturated polyol esters areprepared from one or more unsaturated polyol esters. As used herein, theterm “unsaturated polyol ester” refers to a compound having two or morehydroxyl groups wherein at least one of the hydroxyl groups is in theform of an ester and wherein the ester has an organic group including atleast one carbon-carbon double bond. In many embodiments, theunsaturated polyol ester can be represented by the general structure(I):

-   -   where n≧1;    -   m≧0;    -   p≧_0;    -   (n+m+p)≧2;    -   R is an organic group;    -   R′ is an organic group having at least one carbon-carbon    -   double bond; and    -   R″ is a saturated organic group.

In many embodiments of the invention, the unsaturated polyol ester is anunsaturated polyol ester of glycerol. Unsaturated polyol esters ofglycerol have the general structure (II):

where —X, —Y, and —Z are independently selected from the groupconsisting of:

-   -   —OH; —(O—C(═O)—R′); and —(O—C(═O)—R″);        -   where —W is an organic group having at least one            carbon-carbon double bond and —R″ is a saturated organic            group.

In structure (II), at least one of —X, —Y, or —Z is —(O—C(═O)—R′).

In some embodiments, W is a straight or branched chain hydrocarbonhaving about 50 or less carbon atoms (e.g., about 36 or less carbonatoms or about 26 or less carbon atoms) and at least one carbon-carbondouble bond in its chain. In some embodiments, W is a straight orbranched chain hydrocarbon having about 6 carbon atoms or greater (e.g.,about 10 carbon atoms or greater or about 12 carbon atoms or greater)and at least one carbon-carbon double bond in its chain. In someembodiments, R′ may have two or more carbon-carbon double bonds in itschain. In other embodiments, R′ may have three or more double bonds inits chain. In exemplary embodiments, R′ has 17 carbon atoms and 1 to 3carbon-carbon double bonds in its chain. Representative examples of R′include:

—(CH₂)₇CH═CH—(CH₂)₇—CH₃;

—(CH₂)₇CH═CH—CH₂—CH═CH—(CH₂)₄—CH₃; and

—(CH₂)₇CH═CH—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH₃.

In some embodiments, R″ is a saturated straight or branched chainhydrocarbon having about 50 or less carbon atoms (e.g., about 36 or lesscarbon atoms or about 26 or less carbon atoms). In some embodiments, R″is a saturated straight or branched chain hydrocarbon having about 6carbon atoms or greater (e.g., about 10 carbon atoms or greater or about12 carbon atoms or greater. In exemplary embodiments, R″ has 15 carbonatoms or 17 carbon atoms.

Sources of unsaturated polyol esters of glycerol include synthesizedoils, natural oils (e.g., vegetable oils, algae oils, and animal fats),combinations of these, and the like. Representative examples ofvegetable oils include canola oil, rapeseed oil, coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,castor oil, combinations of these, and the like. Representative examplesof animal fats include lard, tallow, chicken fat, yellow grease, fishoil, combinations of these, and the like. A representative example of asynthesized oil includes tall oil, which is a byproduct of wood pulpmanufacture.

In an exemplary embodiment, the vegetable oil is soybean oil, forexample, refined, bleached, and deodorized soybean oil (i.e., RBDsoybean oil). Soybean oil is an unsaturated polyol ester of glycerolthat typically comprises about 95% weight or greater (e.g., 99% weightor greater) triglycerides of fatty acids. Major fatty acids in thepolyol esters of soybean oil include saturated fatty acids, for example,palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid),and unsaturated fatty acids, for example, oleic acid (9-octadecenoicacid), linoleic acid (9, 12-octadecadienoic acid), and linolenic acid(9,12,15-octadecatrienoic acid). Soybean oil is a highly unsaturatedvegetable oil with many of the triglyceride molecules having at leasttwo unsaturated fatty acids (i.e., a polyunsaturated triglyceride).

In exemplary embodiments, an unsaturated polyol ester isself-metathesized in the presence of a metathesis catalyst to form ametathesized composition. In many embodiments, the metathesizedcomposition comprises one or more of: metathesis monomers, metathesisdimers, metathesis trimers, metathesis tetramers, metathesis pentamers,and higher order metathesis oligomers (e.g., metathesis hexamers). Ametathesis dimer refers to a compound formed when two unsaturated polyolester molecules are covalently bonded to one another by aself-metathesis reaction. In many embodiments, the molecular weight ofthe metathesis dimer is greater than the molecular weight of theindividual unsaturated polyol ester molecules from which the dimer isformed. A metathesis trimer refers to a compound formed when threeunsaturated polyol ester molecules are covalently bonded together bymetathesis reactions. In many embodiments, a metathesis trimer is formedby the cross-metathesis of a metathesis dimer with an unsaturated polyolester. A metathesis tetramer refers to a compound formed when fourunsaturated polyol ester molecules are covalently bonded together bymetathesis reactions. In many embodiments, a metathesis tetramer isformed by the cross-metathesis of a metathesis trimer with anunsaturated polyol ester. Metathesis tetramers may also be formed, forexample, by the cross-metathesis of two metathesis dimers. Higher ordermetathesis products may also be formed. For example, metathesispentamers and metathesis hexamers may also be formed.

An exemplary metathesis reaction scheme is shown in FIGS. 1-1B. As shownin FIG. 1, triglyceride 30 and triglyceride 32 are self metathesized inthe presence of a metathesis catalyst 34 to form metathesis dimer 36 andinternal olefin 38. As shown in FIG. 1A, metathesis dimer 36 may furtherreact with another triglyceride molecule 30 to form metathesis trimer 40and internal olefin 42. As shown in FIG. 1B, metathesis trimer 40 mayfurther react with another triglyceride molecule 30 to form metathesistetramer 44 and internal olefin 46. In this way, the self-metathesisresults in the formation of a distribution of metathesis monomers,metathesis dimers, metathesis trimers, metathesis tetramers, and higherorder metathesis oligomers. Also typically present are metathesismonomers, which may comprise unreacted triglyceride, or triglyceridethat has reacted in the metathesis reaction but has not formed anoligomer. The self-metathesis reaction also results in the formation ofintenal olefin compounds that may be linear or cyclic. FIG. 1C showsrepresentative examples of certain linear and cyclic internal olefins38, 42, 46 that may be formed during a self-metathesis reaction. If themetathesized polyol ester is hydrogenated, the linear and cyclic olefinswould typically be converted to the corresponding saturated linear andcyclic hydrocarbons. The linear/cyclic olefins and saturatedlinear/cyclic hydrocarbons may remain in the metathesized polyol esteror they may be removed or partially removed from the metathesized polyolester using known stripping techniques. It should be understood thatFIG. 1 provides merely exemplary embodiments of metathesis reactionschemes and compositions that may result therefrom.

The relative amounts of monomers, dimers, trimers, tetramers, pentamers,and higher order oligomers may be determined by chemical analysis of themetathesized polyol ester including, for example, by liquidchromatography, specifically gel permeation chromatography (GPC). Forexample, the relative amount of monomers, dimers, trimers, tetramers andhigher unit oligomers may be characterized, for example, in terms of“area %” or wt. %. That is, an area percentage of a GPC chromatographcan be correlated to weight percentage. In some embodiments, themetathesized unsaturated polyol ester comprises at least about 30 area %or wt. % tetramers and/or other higher unit oligomers or at least about40 area % or wt. % tetramers and/or other higher unit oligomers. In someembodiments, the metathesized unsaturated polyol ester comprises no morethan about 60 area % or wt. % tetramers and/or other higher unitoligomers or no more than about 50 area % or wt. % tetramers and/orother higher unit oligomers. In other embodiments, the metathesizedunsaturated polyol ester comprises no more than about 1 area % or wt. %tetramers and/or other higher unit oligomers. In some embodiments, themetathesized unsaturated polyol ester comprises at least about 5 area %or wt. % dimers or at least about 15 area % or wt. % dimers. In someembodiments, the metathesized unsaturated polyol ester comprises no morethan about 25 area % or wt. % dimers. In some of these embodiments, themetathesized unsaturated polyol ester comprises no more than about 20area % or wt. % dimers or no more than about 10 area % or wt. % dimers.In some embodiments, the metathesized unsaturated polyol ester comprisesat least 1 area % or wt. % trimers. In some of these embodiments, themetathesized unsaturated polyol ester comprises at least about 10 area %or wt. % trimers. In some embodiments, the metathesized unsaturatedpolyol ester comprises no more than about 20 area % or wt. % trimers orno more than about 10 area % or wt. % trimers. According to some ofthese embodiments, the metathesized unsaturated polyol ester comprisesno more than 1 area % or wt. % trimers.

In some embodiments, the unsaturated polyol ester is partiallyhydrogenated before being metathesized. For example, in someembodiments, the soybean oil is partially hydrogenated to achieve aniodine value (IV) of about 120 or less before subjecting the partiallyhydrogenated soybean oil to metathesis.

In some embodiments, the hydrogenated metathesized polyol ester has aniodine value (IV) of about 100 or less, for example, about 90 or less,about 80 or less, about 70 or less, about 60 or less, about 50 or less,about 40 or less, about 30 or less, about 20 or less, about 10 or lessor about 5 or less.

Method of Making Metathesized Unsaturated Polyol Ester:

The self-metathesis of unsaturated polyol esters is typically conductedin the presence of a catalytically effective amount of a metathesiscatalyst. The term “metathesis catalyst” includes any catalyst orcatalyst system that catalyzes a metathesis reaction. Any known orfuture-developed metathesis catalyst may be used, alone or incombination with one or more additional catalysts. Exemplary metathesiscatalysts include metal carbene catalysts based upon transition metals,for example, ruthenium, molybdenum, osmium, chromium, rhenium, andtungsten. Referring to FIG. 2, exemplary ruthenium-based metathesiscatalysts include those represented by structures 12 (commonly known asGrubbs's catalyst), 14 and 16. Referring to FIG. 3, structures 18, 20,22, 24, 26, and 28 represent additional ruthenium-based metathesiscatalysts. Referring to FIG. 4, structures 60, 62, 64, 66, and 68represent additional ruthenium-based metathesis catalysts. Referring toFIG. 5, catalysts C627, C682, C697, C712, and C827 represent stilladditional ruthenium-based catalysts. Referring to FIG. 6, generalstructures 50 and 52 represent additional ruthenium-based metathesiscatalysts of the type reported in Chemical & Engineering News; Feb. 12,2007, at pages 37-47. In the structures of FIGS. 2-6, Ph is phenyl, Mesis mesityl, py is pyridine, Cp is cyclopentyl, and Cy is cyclohexyl.Techniques for using the metathesis catalysts are known in the art (see,for example, U.S. Pat. Nos. 7,102,047; 6,794,534; 6,696,597; 6,414,097;6,306,988; 5,922,863; 5,750,815; and metathesis catalysts with ligandsin U.S. Publication No. 2007/0004917 A1). Metathesis catalysts as shown,for example, in FIGS. 2-5 are manufactured by Materia, Inc. (Pasadena,Calif.).

Additional exemplary metathesis catalysts include, without limitation,metal carbene complexes selected from the group consisting ofmolybdenum, osmium, chromium, rhenium, and tungsten. The term “complex”refers to a metal atom, such as a transition metal atom, with at leastone ligand or complexing agent coordinated or bound thereto. Such aligand typically is a Lewis base in metal carbene complexes useful foralkyne- or alkene-metathesis. Typical examples of such ligands includephosphines, halides and stabilized carbenes. Some metathesis catalystsmay employ plural metals or metal co-catalysts (e.g., a catalystcomprising a tungsten halide, a tetraalkyl tin compound, and anorganoaluminum compound).

An immobilized catalyst can be used for the metathesis process. Animmobilized catalyst is a system comprising a catalyst and a support,the catalyst associated with the support. Exemplary associations betweenthe catalyst and the support may occur by way of chemical bonds or weakinteractions (e.g. hydrogen bonds, donor acceptor interactions) betweenthe catalyst, or any portions thereof, and the support or any portionsthereof. Support is intended to include any material suitable to supportthe catalyst. Typically, immobilized catalysts are solid phase catalyststhat act on liquid or gas phase reactants and products. Exemplarysupports are polymers, silica or alumina. Such an immobilized catalystmay be used in a flow process. An immobilized catalyst can simplifypurification of products and recovery of the catalyst so that recyclingthe catalyst may be more convenient.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature and pressure can be selected to producea desired product and to minimize undesirable byproducts. The metathesisprocess may be conducted under an inert atmosphere. Similarly, if areagent is supplied as a gas, an inert gaseous diluent can be used. Theinert atmosphere or inert gaseous diluent typically is an inert gas,meaning that the gas does not interact with the metathesis catalyst tosubstantially impede catalysis. For example, particular inert gases areselected from the group consisting of helium, neon, argon, nitrogen andcombinations thereof.

Similarly, if a solvent is used, the solvent chosen may be selected tobe substantially inert with respect to the metathesis catalyst. Forexample, substantially inert solvents include, without limitation,aromatic hydrocarbons, such as benzene, toluene, xylenes, etc.;halogenated aromatic hydrocarbons, such as chlorobenzene anddichlorobenzene; aliphatic solvents, including pentane, hexane, heptane,cyclohexane, etc.; and chlorinated alkanes, such as dichloromethane,chloroform, dichloroethane, etc.

In certain embodiments, a ligand may be added to the metathesis reactionmixture. In many embodiments using a ligand, the ligand is selected tobe a molecule that stabilizes the catalyst, and may thus provide anincreased turnover number for the catalyst. In some cases the ligand canalter reaction selectivity and product distribution. Examples of ligandsthat can be used include Lewis base ligands, such as, withoutlimitation, trialkylphosphines, for example tricyclohexylphosphine andtributyl phosphine; triarylphosphines, such as triphenylphosphine;diarylalkylphosphines, such as, diphenylcyclohexylphosphine; pyridines,such as 2,6-dimethylpyridine, 2,4,6-trimethylpyridine; as well as otherLewis basic ligands, such as phosphine oxides and phosphinites.Additives may also be present during metathesis that increase catalystlifetime.

Any useful amount of the selected metathesis catalyst can be used in theprocess. For example, the molar ratio of the unsaturated polyol ester tocatalyst may range from about 5:1 to about 10,000,000:1 or from about50:1 to 500,000:1. In some embodiments, an amount of about 1 to about 10ppm, or about 2 ppm to about 5 ppm, of the metathesis catalyst perdouble bond of the starting composition (i.e., on a mole/mole basis) isused.

The metathesis reaction temperature may be a rate-controlling variablewhere the temperature is selected to provide a desired product at anacceptable rate. The metathesis temperature may be greater than −40° C.,may be greater than about −20° C., and is typically greater than about0° C. or greater than about 20° C. Typically, the metathesis reactiontemperature is less than about 150° C., typically less than about 120°C. An exemplary temperature range for the metathesis reaction rangesfrom about 20° C. to about 120° C.

The metathesis reaction can be run under any desired pressure.Typically, it will be desirable to maintain a total pressure that ishigh enough to keep the cross-metathesis reagent in solution. Therefore,as the molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than about 10 kPa, in some embodiments greater than about30 kP, or greater than about 100 kPa. Typically, the reaction pressureis no more than about 7000 kPa, in some embodiments no more than about3000 kPa. An exemplary pressure range for the metathesis reaction isfrom about 100 kPa to about 3000 kPa.

In some embodiments, the metathesis reaction is catalyzed by a systemcontaining both a transition and a non-transition metal component. Themost active and largest number of catalyst systems are derived fromGroup VI A transition metals, for example, tungsten and molybdenum.

Hydrogenation:

In some embodiments, the unsaturated polyol ester is partiallyhydrogenated before it is subjected to the metathesis reaction. Partialhydrogenation of the unsaturated polyol ester reduces the number ofdouble bonds that are available for in the subsequent metathesisreaction. In some embodiments, the unsaturated polyol ester ismetathesized to form a metathesized unsaturated polyol ester, and themetathesized unsaturated polyol ester is then hydrogenated (e.g.,partially or fully hydrogenated) to form a hydrogenated metathesizedunsaturated polyol ester.

Hydrogenation may be conducted according to any known method forhydrogenating double bond-containing compounds such as vegetable oils.In some embodiments, the unsaturated polyol ester or metathesizedunsaturated polyol ester is hydrogenated in the presence of a nickelcatalyst that has been chemically reduced with hydrogen to an activestate. Commercial examples of supported nickel hydrogenation catalystsinclude those available under the trade designations “NYSOFACT”,“NYSOSEL”, and “NI 5248 D” (from Englehard Corporation, Iselin, N.H.).Additional supported nickel hydrogenation catalysts include thosecommercially available under the trade designations “PRICAT 9910”,“PRICAT 9920”, “PRICAT 9908”, “PRICAT 9936” (from Johnson MattheyCatalysts, Ward Hill, Mass.).

In some embodiments, the hydrogenation catalyst comprising, for example,nickel, copper, palladium, platinum, molybdenum, iron, ruthenium,osmium, rhodium, or iridium. Combinations of metals may also be used.Useful catalyst may be heterogeneous or homogeneous. In someembodiments, the catalysts are supported nickel or sponge nickel typecatalysts.

In some embodiments, the hydrogenation catalyst comprises nickel thathas been chemically reduced with hydrogen to an active state (i.e.,reduced nickel) provided on a support. In some embodiments, the supportcomprises porous silica (e.g., kieselguhr, infusorial, diatomaceous, orsiliceous earth) or alumina. The catalysts are characterized by a highnickel surface area per gram of nickel.

In some embodiments, the particles of supported nickel catalyst aredispersed in a protective medium comprising hardened triacylglyceride,edible oil, or tallow. In an exemplary embodiment, the supported nickelcatalyst is dispersed in the protective medium at a level of about 22wt. % nickel.

In some embodiments, the supported nickel catalysts are of the typereported in U.S. Pat. No. 3,351,566 (Taylor et al.). These catalystscomprise solid nickel-silica having a stabilized high nickel surfacearea of 45 to 60 sq. meters per gram and a total surface area of 225 to300 sq. meters per gram. The catalysts are prepared by precipitating thenickel and silicate ions from solution such as nickel hydrosilicate ontoporous silica particles in such proportions that the activated catalystcontains 25 wt. % to 50 wt. % nickel and a total silica content of 30wt. % to 90 wt %. The particles are activated by calcining in air at600° F. to 900° F., then reducing with hydrogen.

Useful catalysts having a high nickel content are described in EP 0 168091, wherein the catalyst is made by precipitation of a nickel compound.A soluble aluminum compound is added to the slurry of the precipitatednickel compound while the precipitate is maturing. After reduction ofthe resultant catalyst precursor, the reduced catalyst typically has anickel surface area of the order of 90 to 150 sq. m per gram of totalnickel. The catalysts have a nickel/aluminum atomic ratio in the rangeof 2 to 10 and have a total nickel content of more than about 66% byweight.

Useful high activity nickel/alumina/silica catalysts are described in EP0 167 201. The reduced catalysts have a high nickel surface area pergram of total nickel in the catalyst.

Useful nickel/silica hydrogenation catalysts are described in U.S. Pat.No. 6,846,772. The catalysts are produced by heating a slurry ofparticulate silica (e.g. kieselguhr) in an aqueous nickel aminecarbonate solution for a total period of at least 200 minutes at a pHabove 7.5, followed by filtration, washing, drying, and optionallycalcination. The nickel/silica hydrogenation catalysts are reported tohave improved filtration properties. U.S. Pat. No. 4,490,480 reportshigh surface area nickel/alumina hydrogenation catalysts having a totalnickel content of 5% to 40% wt.

Commercial examples of supported nickel hydrogenation catalysts includethose available under the trade designations “NYSOFACT”, “NYSOSEL”, and“NI 5248 D” (from Englehard Corporation, Iselin, N.H.). Additionalsupported nickel hydrogenation catalysts include those commerciallyavailable under the trade designations “PRICAT 9910”, “PRICAT 9920”,“PRICAT 9908”, “PRICAT 9936” (from Johnson Matthey Catalysts, Ward Hill,Mass.).

Hydrogenation may be carried out in a batch or in a continuous processand may be partial hydrogenation or complete hydrogenation. In arepresentative batch process, a vacuum is pulled on the headspace of astirred reaction vessel and the reaction vessel is charged with thematerial to be hydrogenated (e.g., RBD soybean oil or metathesized RBDsoybean oil). The material is then heated to a desired temperature.Typically, the temperature ranges from about 50° C. to 350° C., forexample, about 100° C. to 300° C. or about 150° C. to 250° C. Thedesired temperature may vary, for example, with hydrogen gas pressure.Typically, a higher gas pressure will require a lower temperature. In aseparate container, the hydrogenation catalyst is weighed into a mixingvessel and is slurried in a small amount of the material to behydrogenated (e.g., RBD soybean oil or metathesized RBD soybean oil).When the material to be hydrogenated reaches the desired temperature,the slurry of hydrogenation catalyst is added to the reaction vessel.Hydrogen gas is then pumped into the reaction vessel to achieve adesired pressure of H₂ gas. Typically, the H₂ gas pressure ranges fromabout 15 to 3000 psig, for example, about 15 psig to 90 psig. As the gaspressure increases, more specialized high-pressure processing equipmentmay be required. Under these conditions the hydrogenation reactionbegins and the temperature is allowed to increase to the desiredhydrogenation temperature (e.g., about 120° C. to 200° C.) where it ismaintained by cooling the reaction mass, for example, with coolingcoils. When the desired degree of hydrogenation is reached, the reactionmass is cooled to the desired filtration temperature.

The amount of hydrogenation catalysts is typically selected in view of anumber of factors including, for example, the type of hydrogenationcatalyst used, the amount of hydrogenation catalyst used, the degree ofunsaturation in the material to be hydrogenated, the desired rate ofhydrogenation, the desired degree of hydrogenation (e.g., as measure byiodine value (IV)), the purity of the reagent, and the H₂ gas pressure.In some embodiments, the hydrogenation catalyst is used in an amount ofabout 10 wt. % or less, for example, about 5 wt. % or less or about 1wt. % or less.

After hydrogenation, the hydrogenation catalyst may be removed from thehydrogenated product using known techniques, for example, by filtration.In some embodiments, the hydrogenation catalyst is removed using a plateand frame filter such as those commercially available from SparklerFilters, Inc., Conroe Tex. In some embodiments, the filtration isperformed with the assistance of pressure or a vacuum. In order toimprove filtering performance, a filter aid may be used. A filter aidmay be added to the metathesized product directly or it may be appliedto the filter. Representative examples of filtering aids includediatomaceous earth, silica, alumina, and carbon. Typically, thefiltering aid is used in an amount of about 10 wt. % or less, forexample, about 5 wt. % or less or about 1 wt. % or less. Other filteringtechniques and filtering aids may also be employed to remove the usedhydrogenation catalyst. In other embodiments the hydrogenation catalystis removed using centrifugation followed by decantation of the product.

Petrolatum-Like Compositions:

Petrolatum-like compositions of the invention comprise a metathesizedunsaturated polyol ester. In some embodiments, the metathesizedunsaturated polyol ester is hydrogenated. Hydrogenation may be partialhydrogenation or full hydrogenation. The degree of hydrogenation may becontrolled in order to achieve the desired properties. For example, asthe degree of hydrogenation increases, the melting point of thecomposition increases providing a composition that is more solid-like(i.e., harder) at room temperature.

In some embodiments, the hydrogenated metathesized unsaturated polyolester itself has petrolatum-like properties. In some embodiments, thepetrolatum-like composition comprises a mixture of: (a) a metathesizedunsaturated polyol ester; and (b) a polyol ester. In many embodiments,the metathesized unsaturated polyol ester is hydrogenated (e.g.,partially hydrogenated or fully hydrogenated). Typically, in theseembodiments, the hydrogenated metathesized unsaturated polyol ester is asolid or a high viscosity semi-solid (e.g., a wax) at room temperature,and the polyol ester is a liquid at room temperature. When mixedtogether, the two materials form a composition that has petrolatum-likeproperties.

The hydrogenated metathesized unsaturated polyol ester and the polyolester may be mixed in desired amounts to form a petrolatum-likecomposition of the invention having the desired petrolatum-likeproperties. Typically, as the amount of hydrogenated metathesized polyolester in the composition increases, the viscosity of the resultingpetrolatum-like composition increases. In some embodiments, thehydrogenated metathesized polyol ester is present in an amount up toabout 75% wt., for example, up to about 50% wt., up to about 40% wt., upto about 35% wt., up to about 30% wt., or up to about 25% wt. Inexemplary embodiments, the hydrogenated metathesized polyol ester ispresent in an amount from about 5% wt. to about 50% wt. or from about 5%wt. to 25% wt.

Representative examples of polyol esters for use in the petrolatum-likecompositions include natural oils, for example, vegetable oils, algaeoils, animal fats, or mixtures thereof. Representative examples ofvegetable oils include canola oil, rapeseed oil, coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,castor oil, and the like, and mixtures thereof. Examples of animal fatsinclude lard, tallow, chicken fat (yellow grease), fish oil, andmixtures thereof. Preferred natural oils are liquids at room temperatureand are stable over time. In an exemplary embodiment, the natural oil isrefined, bleached, and deodorized soybean oil (i.e., RBD soybean oil).Suitable RBD soybean oil can be obtained commercially from Cargill,Incorporated. (Minneapolis, Minn.).

In some embodiments, the natural oil may be hydrogenated (e.g., fully orpartially hydrogenated) in order to improve the stability of the oil orto modify its viscosity or other properties. Representative techniquesfor hydrogenating natural oils are known in the art and are discussedherein. For example, hydrogenation of certain vegetable oils is reportedin Chapter 11 of Bailey, A. E.; Baileys Industrial Oil and Fat Products;Volume 2: Edible Oil & Fat Products: Oils and Oil Seeds; 5^(th) Edition(1996) edited by Y. H. Hui (ISBN 0-471-59426-1). In some embodiments,the natural oil is RBD soybean oil that has been lightly hydrogenated toachieve an Iodine Value (IV) of about 100 or greater, for example, about100 to about 110. Suitable lightly hydrogenated RBD soybean oil iscommercially available from Cargill, Incorporated (Minneapolis, Minn.).

In some embodiments, the natural oil is winterized. Winterization refersto the process of: (1) removing waxes and other non-triglycerideconstituents, (2) removing naturally occurring high-meltingtriglycerides, and (3) removing high-melting triglycerides formed duringpartial hydrogenation. Winterization may be accomplished by knownmethods including, for example, cooling the oil at a controlled rate inorder to cause crystallization of the higher melting components that areto be removed from the oil. The crystallized high melting components arethen removed from the oil by filtration resulting in winterized oil.Winterized soybean oil is commercially available from Cargill,Incorporated (Minneapolis, Minn.).

In some embodiments, the polyol ester may comprise a mixture of two ormore natural oils. For example, in some embodiments, the polyol estermay comprise a mixture of fully-hydrogenated soybean oil and partiallyor non-hydrogenated soybean oil. In other embodiments, the polyol estermay comprise a mixture of partially hydrogenated soybean oil andnon-hydrogenated soybean oil. In yet other embodiments, the polyol estermay comprise a mixture of two or more different natural oils, forexample, a mixture of soybean oil and castor oil. In exemplaryembodiments, the petrolatum-like composition comprises a mixture of: (i)a hydrogenated metathesized vegetable oil; and (ii) a vegetable oil. Forexample, in some embodiments, the petrolatum-like composition comprisesa mixture of: (i) hydrogenated metathesized soybean oil (HMSBO); and(ii) soybean oil. In some embodiments, the soybean oil is partiallyhydrogenated, for example, having an iodine value (IV) of about 80 to120.

In some embodiments, the petrolatum-like compositions of the inventionhave an iodine value (IV) that ranges from about 5 to about 100, moretypically ranging from about 20 to about 100. In some embodiments, theiodine value ranges from about 70 to about 90.

In some embodiments, the petrolatum-like compositions have a conepenetration @ 77° F. (25° C.) (ASTM D-937) that is similar topetroleum-derived petrolatum. For example, in some embodiments, thecompositions may have a cone penetration @ 77° F. (25° C.) of about 100dmm to about 300 dmm. In exemplary embodiments, the compositions have acone penetration @ 77° F. (25° C.) of about 150 dmm to about 160 dmm.

In some embodiments, the petrolatum-like compositions have a congealingpoint (ASTM D-938) that is similar to petroleum-derived petrolatum. Forexample, in some embodiments the compositions may have a congealingpoint of about 100° F. to about 140° F. (37.8° C. to 60° C.). Inexemplary embodiments, the compositions have a congealing point of about105° F. to about 135° F. (40.6° C. to 57.2° C.).

In some embodiments, the petrolatum-like compositions have a drop meltpoint (ASTM D-127) that is similar to petroleum-derived petrolatum. Forexample, in some embodiments the compositions may have a drop melt pointof about 100° F. to about 150° F. (37.8° C. to 65.6° C.).

In some embodiments, the petrolatum-like compositions have a viscosityat 210° F. (ASTM D-445 and D-2161) that is similar to that ofpetroleum-derived petrolatum. For example, in some embodiments thecompositions have a kinematic viscosity of about 100 SUS or less, moretypically about 40 SUS to about 90 SUS, or about 55 to about 80 SUS.

Method of Manufacturing Petrolatum-Like Compositions:

A petrolatum-like composition comprising a mixture of (i) a hydrogenatedmetathesized unsaturated polyol ester, and (ii) a polyol ester may beprepared, for example, by the following general process. First, thepolyol ester (e.g., soybean oil) is heated to a temperature of about100° F. to 150° F. (37.8° C. to 65.6° C.). Next, the hydrogenatedmetathesized unsaturated polyol ester (e.g., hydrogenated metathesizedsoybean oil) is added to the polyol ester and the two materials aremixed together to form a uniform composition. Optional ingredients suchas stabilizers may be added in some embodiments. After thoroughlymixing, the resulting mixture is allowed to cool upon which it formspetrolatum-like composition.

Stabilizers:

In some embodiments, the petrolatum-like compositions further includesone or more stabilizers. Representative stabilizers include antioxidants(e.g., tocopherols or BHT) or emulsifiers. Typically, stabilizers areadded in an amount less than about 2% wt. although other amounts mayalso be useful.

Representative Applications of Petrolatum-Like Compositions:

Petrolatum-like compositions of the invention may be suitable in a widevariety of applications including, for example, applications wherepetroleum-derived petrolatum compositions have historically been used.Representative examples of typical applications include personal careitems (e.g., cosmetics, lip balms, lipsticks, perfumes, hand cleaners,hair dressings, ointments, sun care products, moisturizers,pharmaceutical ointments); plastics (e.g., a processing aid for PVC);food (e.g., cheese coatings, baking grease); telecommunications (e.g.,cable filling or flooding compounds); industrial applications (e.g.,grain dust suppressant, rust preventative coatings, adhesives, toiletboil rings, bone guard, and textile coatings).

Emulsions Comprising Petrolatum-Like Compositions

In some embodiments, the invention provides emulsions comprisinghydrogenated metathesized unsaturated polyol esters. As used herein, theterm “emulsion” refers to a stable dispersion of two or more immiscibleliquids. In the emulsion, a first liquid (the “dispersed phase”) isdispersed and held in suspension in the second liquid (the “continuousphase”) with an emulsifier. Emulsions of the invention may beoil-in-water emulsions or water-in-oil emulsions. Oil-in-water emulsionshave a dispersed phase comprising an organic material (e.g., an oily orwaxy material) and a continuous phase comprising water. Water-in-oilemulsions have a dispersed phase comprising water and a continuous phasecomprising an organic material (e.g., an oily or waxy material).

In some embodiments, oil-in-water emulsions of the invention comprise adispersed phase comprising a hydrogenated metathesized unsaturatedpolyol ester. In other embodiments, the oil-in-water emulsions comprisea dispersed phase that comprises a mixture comprising: (i) ahydrogenated metathesized unsaturated polyol ester; and (ii) a polyolester. In many embodiments, the dispersed phase comprises a materialthat has petrolatum-like properties. In other embodiments, the dispersedphase comprises a wax.

In some embodiments, the oil-in-water emulsions of the inventioncomprise about 60% wt. or less dispersed phase and about 40% wt. orgreater continuous phase. In other embodiments, the oil-in-wateremulsions of the invention comprise about 1% wt. to about 60% wt.dispersed phase and about 40% wt. to about 99% wt. continuous phase. Inexemplary embodiments, the emulsions comprise about 1% wt. to about 30%wt. dispersed phase and about 70% wt. to about 99% wt. continuous phase.

In some embodiments, the dispersed phase of the emulsion has a particlesize of about 1 μm or less. A small particle size promotes thorough,homogeneous incorporation with other ingredients that may be present ina formulation comprising the emulsion.

Suitable emulsifiers and surfactants include nonionic emulsifiers, ionicemulsifiers (e.g., anionic or cationic emulsifiers), and amphotericemulsifiers. Nonionic emulsifers stabilize via a steric mechanismwhereas ionic emulsifiers stabilize via an electrostatic mechanism. Insome embodiments, a combination of two or more emulsifiers is used. Forexample, in some embodiments, anionic and nonionic emulsifiers arecombined to provide increased stability to the emulsion.

Examples of nonionic surfactants include sorbitan esters such assorbitan monolaurate, sorbitan monooleate, sorbitan monoisostearate;polyoxyethylene sorbitan esters such as polyoxyethylene sorbitanmonoisostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylenesorbitan monooleate; glycerol ethers such as glycerol monoisostearate,glycerol monomyristate; polyoxyethylene glycerol ethers such aspolyoxyethylene glycerol monoisostearate, polyoxyethylene glycerolmonomyristate; polyglycerin fatty acid esters such as diglycerylmonostearate, decaglyceryl decaisostearate, diglyceryl diisostearate;glycerin fatty acid esters such as glyceryl monocaprate, glycerylmonolaurate, glycerylmonomyristate, glycerylmonopalminate,glycerylmonooleate, glyceryl monostearate, glyceryl monolinoleate,glyceryl monoisostearate, glyceryl monodilinoleate, glycerylmonodicaprate; polyoxyethylene glycerin fatty acid esters such aspolyoxyethylene glyceryl monomyristate, polyoxyethylene glycerylmonooleate, polyoxyethylene glyceryl monostearate; polyoxyethylenebranched alkyl ethers such as polyoxyethylene octyldodecyl alcohol,polyoxyethylene-2-decyltetradecyl alcohol; polyoxyethylene alkyl etherssuch as polyoxyethylene oleyl alcohol ether, polyoxyethylene cetylalcohol ether; polyoxyethylene hydrogenated castor oil fatty acid esterssuch as polyoxyethylene hydrogenated castor oil, polyoxyethylenedihydrocholesterol ether, polyoxyethylene hydrogenated castor oilisostearate; polyoxyethylene alkyl aryl ethers such as polyoxyethyleneoctyl phenol ether. Representative examples of nonionic emulsifiersinclude ethoxylated cetaryl alcohol mixed with cetaryl alcohol (e.g.,“PROMULGEN D” from Noveon, Cleveland Ohio) and glyceryl stearate (e.g.,“ARLACEL 165” from Unichema Chemi BV, Netherlands).

Examples of anionic surfactants include salts of higher fatty acids suchas oleic acid, stearic acid, isostearic acid, palmitic acid, myristicacid, behenic acid, for example, diethanolamine salts, triethanolaminesalts, amino acid salts, potassium salts, sodium salts, ether carboxylicacid alkali salts, N-acylamino acid salts, N-acyl sarcosinates, higheralkyl sulfonates.

Examples of cationic or amphoteric surfactants include alkyl quaternaryammonium salts, polyamines and alkyl amine salts. Examples of colloidalemulsifiers include clay/lignosulfonates and clay/naphthalenesulfonates.

In some embodiments, the emulsion has a pH ranging from about 6 to 7,more typically ranging from about 6.0 to 6.5. Typically, the pH of theemulsion is adjusted to be within about 1 pH unit of a material that theemulsion is being added to. The pH of the emulsion may be adjusted, forexample, by adding aqueous ammonia solution (i.e., to increase pH) oracetic acid (to reduce pH).

In some embodiments, water-in-oil emulsions of the invention comprise acontinuous phase comprising a hydrogenated metathesized unsaturatedpolyol ester. For example, the continuous phase may comprise a mixtureof: (i) a hydrogenated metathesized unsaturated polyol ester; and (ii) apolyol ester. The continuous phase may have petrolatum-like propertiesor may be a wax.

In many embodiments, the water-in-oil emulsions comprise from about 30wt. % to about 70 wt. % continuous (i.e., oil) phase; about 20 wt. % toabout 68 wt. % dispersed (i.e.,) phase; and about 2 wt. % to about 10wt. % emulsifier. Representative examples of emulsifiers forwater-in-oil emulsions include polyvalent soap emulsifiers combined withnon-ionic PEG esters, silicone-based emulsifiers, and non-ionicemulsifiers.

Method of Manufacturing Emulsions:

Emulsions of the invention may be manufactured according to knownmethods in the art for manufacturing oil-in-water emulsions andwater-in-oil emulsions. For oil-in-water emulsions, the water andemulsifier(s) are mixed until uniform. The mixture is then heated, forexample, to about 80° C. and molten wax (e.g., hydrogenated metathesizedunsaturated polyol ester) is added and mixed into the water/emulsifierphase until a uniform dispersion of the wax is formed. In manyembodiments, a homogenizer or high shear mixer is used to reduce theparticle size to a size where the emulsion is stable (e.g., about 0.1 to1.5 microns). The emulsion may then be shock chilled to set theparticles at the desired particle size.

Water-in-oil emulsions are typically prepared by a two-part process. Thewater phase and the oil phase are heated separately (e.g., about 70°C.-75° C. (about 5° to 10° C. about the melting point of the highestmelting component in the formula)). The water phase and the oil phaseare then mixed together. When the mixture is uniform, the mixture isslowly cooled to about 40° C. to 45° C. and other ingredients (e.g.,fragrances, etc.) are added.

Applications of Emulsions:

Emulsions of the invention may be suitable in a wide variety ofapplications including, but not limited to, applications wherepetroleum-derived petrolatum or paraffin waxes have historically beenused. Representative uses for the emulsions of the invention include inbuilding materials (e.g., coatings for oriented strand board (OSB) ormedium density fiberboard, lumber coatings); metal coatings (e.g., slipcoating for cans, coil coatings); inks (e.g., additive to improve rub orscuff resistance in water based inks); fiberglass (e.g., antiblock orlubricant); molded latex articles (e.g., mold release for gloves orcondoms); textiles (e.g., sizing agent or thread lubricant); floorfinishes (e.g., additive to impart rub resistance); flexible films(e.g., processing aid); coatings (e.g., to add water repellency to deckstains or wood varnishes); polishes (e.g., hard surface, floor or autopolishes); and fruit/vegetable coatings (e.g., as a moisture barriercoating); cosmetic and personal care formulations (e.g., face, hand andbody lotions/creams, lip care products, hair care products as amoisturizer or moisture barrier coating). Water-in-oil emulsions may besuitable for use, for example, in water-resistant sunscreens and innight creams.

The emulsions of the invention may be incorporated into formulations bysimple mixing. The fine particle size provides thorough and homogeneousincorporation with other formulation ingredients.

The invention will now be described with reference to the followingnon-limiting examples.

EXAMPLES Example 1 Example 1A Large Batch Metathesis Reaction

In a 50-gallon batch reactor, the soybean oil (87 Kg) was degassedovernight (˜16 hrs) with argon or nitrogen at an estimated rate of 10mL/min. Degassing the soybean oil yields optimal catalyst efficienciesand prevents metathesis catalyst decomposition The oil was then heatedto 70° C. Ruthenium catalyst (C827, 4.2 g, 50 ppm) was added. Themetathesis reaction was run for 2 hours, under an atmosphere of argon.The stir rate was not measured, but stirring was sufficient to cause asmall amount of splash from the baffle. GC analysis of the correspondingmethyl esters indicated 68% conversion. The metathesis catalyst was notremoved prior to hydrogenation.

Metathesis Catalyst Removal Procedure

The metathesis catalyst was removed using THMP which was prepared byadding 245 g of tetrakishydroxymethyl phosphonium chloride (TKC) (1.03mol, Cytec) and 500 mL of isopropyl alcohol (IPA) to a 2 Lround-bottomed flask, degassing the mixture with nitrogen for 20minutes, slowly adding 64 g (1.03 mol, 90% purity, Aldrich) of potassiumhydroxide over 30 minutes to the vigorously stirring solution, whileunder a nitrogen atmosphere, and, after the potassium hydroxide has beenadded, stirring the reaction for an additional 30 minutes. The reactionwas exothermic, and produced THMP, formaldehyde, potassium chloride, andwater. The catalyst was then removed using the THMP by adding 25-100 molequivalents of THMP per mole of ruthenium catalyst, stirring vigorouslyat 60-70° C. for 18 to 24 hours under nitrogen, adding degassed water ormethanol (˜150 mL/L of reaction mixture) and vigorously stirring for 10minutes, and centrifuging the mixture for phase separation. Thistypically removes ruthenium to <1 ppm levels.

The oil may have to be heated to remove the residual water or methanol.The aqueous phase will contain small amounts of IPA, formaldehyde, andpotassium chloride, and will need to be purged or cleaned for recycling.

The second catalyst removal technique involves contacting the metathesismixture with 5 wt % of Pure Flo 80 bleaching clay (i.e., 5 g bleachingclay/100 g metathesis mixture) for 4 hr at 70° C., followed by filteringthe metathesis mixture through a plug of bleaching clay and sand. Thistechnique typically removes ruthenium to <1 ppm levels.

Hydrogenation Procedure

The metathesis product can then be hydrogenated by heating theself-metathesized soybean oil to 350° F., while held under nitrogen,adding 0.4 wt % Ni catalyst to the oil once at 350° F., starting theflow of hydrogen at a pressure of 35 psi, having a hold temperature ofabout 410° F., and checking the reaction at 1 hour to see where the IVis in comparison to target. A 2.5 kg batch may take about 30-45 minutes.After about 2 hours (oil should be fully hydrogenated), nitrogen is putback in the vessel and the oil is cooled. The hydrogenatedself-metathesized soybean oil may then be filtered to remove excesscatalyst.

Example 2

Three sample metathesis products (A, C, and E) were subject tometathesis as described in EXAMPLE 1 to different degrees. These threemetathesis products were hydrogenated, as described in EXAMPLE 1, toform hydrogenated versions of the metathesis products (B, D, and F).

Sample A was prepared starting with unrefined soybean oil (100 g) and100 ppm of catalyst C627. The reaction was run at room temperature for20 hrs and was then warmed to 40° C. for 5 hrs to yield 62% conversion,by GC analysis of the converted methyl ester. The metathesis catalystwas removed with THMP and water prior to hydrogenation.

Sample C was prepared starting with unrefined soybean oil (58 g) and 50ppm of catalyst C627. The reaction was run at room temperature for 22hrs, to yield 14% conversion. The metathesis catalyst was not removedbefore hydrogenation.

Sample E was prepared starting with unrefined soybean oil (68 g) and 50ppm of catalyst C715. Catalyst C715 is the same as catalyst C627, exceptthat it has bromine ligands where C627 has chlorine ligands. Theself-metathesis reaction was run at room temperature for 22 hrs, toyield 27% conversion. The metathesis catalyst was removed with THMP andwater prior to hydrogenation.

Polymer analysis indicated that each of the metathesized samples andtheir corresponding hydrogenated samples (in parentheses) A (B), C (D),and E (F) were reacted to different endpoints. As can be seen in TABLE1, Sample C was the least reacted (i.e., the most triglyceride remained)and Sample A was the most reacted (i.e., lowest triglyceride and highestoligomer concentration). HPSEC analysis indicated Sample B had 21.2%unreacted triglyceride, Sample D had 93.3% unreacted triglyceride, andSample F had 80.8% unreacted triglyceride. Samples A, C, and E hadsimilar HPSEC chromatograms as their corresponding hydrogenated samples.

TABLE 1 A B C D E F Total 75.6 78.7 6.9 6.7 20.5 19.3 OligomersTetramers 46.1 50.7 ND ND 0.5 0.4 and Higher Oligomers Dimers 16.4 16.16.5 6.4 16.5 15.9 Trimers 13.0 12.0 0.4 0.3 3.5 3.0 TAG 24.4 21.2 93.193.3 79.6 80.8

TABLE 2 shows the fatty acid composition of the six samples. The oilcontent is determined by converting the fatty acid methyl esters (FAME)into their triacylglycerol equivalents with the use of an internalstandard, so the values are on a weight percent basis. All theindividual fatty acids were determined by converting the FAME into fattyacid (FA) equivalents and are on a weight basis.

TABLE 2 A B C D E F Trans 13.35 1.36 8.02 0.01 11.49 1.65 (% w/w FA)C18:1 8.06 1.87 20.13 0.11 17.86 2.21 (% w/w FA) C18:2 8.81 0.58 41.64ND 31.78 0.27 (% w/w FA) C18:3 0.12 0.01 4.01 ND 2.26 0.01 (% w/w FA)C18:0 4.03 18.51 4.11 68.12 4.06 50.38 (% w/w FA) Saturated FA 17.1744.69 15.50 83.2 15.59 67.40 (% w/w FA) C6:0 0.01 7.04 ND 1.90 ND 3.21(% w/w FA) C9:0 ND 3.95 0.01 1.05 0.01 1.77 (% w/w) C12:0 0.02 1.17 0.010.29 0.02 0.50 (% w/w) C15:0 0.04 10.70 0.03 2.73 0.03 4.55 (% w/w)

Example 3: Preparation of Petrolatum Compositions

Petrolatum-like compositions suitable for use in cosmetics (e.g., as areplacement for petroleum-derived petrolatum) were prepared by blendingthe metathesis product B of Example 2 with 90 IV soybean oil in variousratios. TABLE 3 shows exemplary compositions.

TABLE 3 Hydrogenated 90 Metathesized IV soybean Soybean Oil oil MeltingPoint Iodine Value of (parts) (parts) ° F. (° C.) Blend Blend 1 5 95100.2 (37.9) 85.7 Blend 2 10 90 105.6 (40.9) 81 Blend 3 15 85 109.9(43.3) 76.1 Blend 4 25 75 115.3 (46.3) 64.1

Example 4

Emulsions

Ingredient List—Dispersed Phase

INGREDIENT DESCRIPTION A 100% HMSBO B 30% HMSBO in 300 Oil C 10% HMSBOin 300 Oil D 10% HMSBO/5% Glycerol in 300 Oil E 100% HSBO F PETROLATUM(Penreco Snow White Petrolatum)

Ingredient List—Other Components

NAME FUNCTION INCI DESIGNATION SUPPLIER CARBOPOL 980 THICKENER CARBOMERNOVEON (2% wt. solution) DISODIUM EDTA CHELATOR DISODIUM EDTA CIBAPROPYLENE FREEZE/THAW GLYCOL STABILIZER PROMULGEN D HYDROPHOBID CETEARYLALCOHOL AMERCHOL EMULSIFIER CETEARETH-20 ARLACEL 165 HYDROPHILLICGLYCERYL STEARATE UNIQEMA EMULSIFIER PEG-100 STEARATE SODIUM PH ADJUSTERSODIUM HYDROXIDE CHEMTECH HYDROXIDE (20% wt. solution) GERMABEN IIPARABEN PROPYLENE GLYCOL ISP SUTTON PRESERVATIVE DIAZOLIDINYL UREAMETHYLPARABEN PROPYLPARABEN WATER WATER

Emulsions 4-A to 4-E were prepared according to the following generalprocedure. The formulations are provided below.

(1) Phase A ingredients were combined together and were heated to 70° C.with mixing.

(2) Separately, phase B ingredients were combined and were heated to 70°C. while mixing. The phase B ingredients were mixed until the wax hadmelted and the phase B was uniform. Phase B ingredients were then addedto the Phase A ingredients.

(3) Phase C was used to adjust the pH of batch to between 6.0 and 6.5.

(4) The batch was then cooled to 40° C. and phase D ingredients wereadded to the batch.

(5) The resulting emulsion was cooled to room temperature while beingmixed.

Example Emulsion 4-A

INGREDIENT PHASE % WT. Batch Size WATER A 62.75 313.75 CARBOPOL A 20.0100.00 980 DISODIUM A 0.10 0.50 EDTA PROPYLENE A 2.0 10.00 GLYCOLPROMULGEN D B 2.0 10.00 DISPERSED B 10.0 50.00 OIL INGREDIENT 4-AARLACEL 165 B 1.5 7.50 SODIUM C 0.65 3.25 HYDROXIDE GERMABEN II D 1.05.00

Example 4-A Characteristics

pH=6.23

Viscosity=50,000 cps (TC spindle @ 5 RPM)

Example Emulsion 4-B

INGREDIENT PHASE % WT. Batch Size WATER A 62.75 313.75 CARBOPOL A 20.0100.00 980 DISODIUM A 0.10 0.50 EDTA PROPYLENE A 2.0 10.00 GLYCOLPROMULGEN D B 2.0 10.00 DISPERSED B 10.0 50.00 OIL INGREDIENT 4-BARLACEL 165 B 1.5 7.50 SODIUM C 0.65 3.25 HYDROXIDE GERMABEN II D 1.05.00

Example 4-B Characteristics

pH=6.01

Viscosity=46,000 cps (TC spindle @ 5 RPM)

Example Emulsion 4-C

INGREDIENT PHASE % WT. Batch Size WATER A 62.75 313.75 CARBOPOL A 20.0100.00 980 DISODIUM A 0.10 0.50 EDTA PROPYLENE A 2.0 10.00 GLYCOLPROMULGEN D B 2.0 10.00 DISPERSED B 10.0 50.00 OIL INGREDIENT 4-CARLACEL 165 B 1.5 7.50 SODIUM C 0.65 3.25 HYDROXIDE GERMABEN II D 1.05.00

Example 4-C Characteristics

pH=6.14

Viscosity=66,000 cps (TC spindle @ 5 RPM)

Example Emulsion 4-D

INGREDIENT PHASE % WT. Batch Size WATER A 62.8 314.00 CARBOPOL A 20.0100.00 980 DISODIUM A 0.10 0.50 EDTA PROPYLENE A 2.0 10.00 GLYCOLPROMULGEN D B 2.0 10.00 DISPERSED B 10.0 50.00 OIL INGREDIENT 4-DARLACEL 165 B 1.5 7.50 SODIUM C 0.60 3.00 HYDROXIDE GERMABEN II D 1.05.00

Example 4-D Characteristics

pH=5.93

Viscosity=58,000 cps (TC spindle @ 5 RPM)

Example Emulsion 4-E

INGREDIENT PHASE % WT. Batch Size WATER A 62.75 313.75 CARBOPOL A 20.0100.00 980 DISODIUM A 0.10 0.50 EDTA PROPYLENE A 2.0 10.00 GLYCOLPROMULGEN D B 2.0 10.00 DISPERSED B 10.0 50.00 OIL INGREDIENT 4-EARLACEL 165 B 1.5 7.50 SODIUM C 0.65 3.25 HYDROXIDE GERMABEN II D 1.05.00

Example 4-E Characteristics

pH=6.37

Viscosity=40,400 cps (TB spindle @ 5 rpm)

Example Emulsion 4-F (Control)

INGREDIENT PHASE % WT. BATCH SIZE WATER A 63.05 315.25 CARBOPOL A 20.0100.00 980 DISODIUM A 0.10 0.50 EDTA PROPYLENE A 2.00 10.00 GLYCOLPROMULGEN D B 2.00 10.00 DISPERSED B 10.0 50.00 OIL INGREDIENT 4-FARLACEL 165 B 1.50 7.50 SODIUM C 0.35 1.75 HYDROXIDE GERMABEN II D 1.05.00

Example 4-F Characteristics

pH=6.34

Viscosity=36,000 cps (TB spindle @ 5 rpm)

Emulsion Stability Study

TABLE 4 Example No. 4-A 4-B 4-C 4-D 4-E 4-F Dispersed A B C D E F PhasePreparation Day 12 Day 8 Day 5 Day 1 Day 28 Day 35 Day Room Temp³ StableStable Stable Stable Stable Stable 3 Freeze- Stable Stable Stable StableStable Stable Thaw Cycles¹ Oven² Stable Stable Stable Stable StableStable ¹During each cycle the sample was frozen at −5° C. for 24 hoursfollowed by being thawed at room temperature for 24 hours. ²Oventemperature was 45° C. ³Stability was tested on Days 28, 35, 44, and 57

-   Observations: Day 28—all samples in oven and room temperature    appeared the same. Samples have not changed in color or odor.    -   Day 35—all samples in the oven and room temperature looked very        stable except Example 4-E which appeared the same but had become        gelatinous after 3 days at 45° C.    -   Day 44—all samples in the oven and room temperature were stable        in color and odor. Example 4-E became gelatinous at room        temperature.

The emulsion compositions 4-A to 4-F were evaluated for use as handcreams. The results are presented in TABLE 5.

TABLE 5 Appearance, Initial application: Length of Emulsion Peak rub-in,tack “play Observations of skin No. behavior Odor (stickiness) time”after application 4-A Grainy Very Tacky and waxy feel Very short A lotof drag but not emulsion strong play time like petrolatum: a anisettedry drag, not greasy, smell but unpleasant 4-B Nice white Fragrant Niceemollient feel, Short play Some drag but silky cream odor; like Nonoticeable tack, time disappears and anisette. little whitening effectleaves skin smooth feeling. Heavier (residual) feel than 4-C, doesn'timpart shine 4-C Nice white Slight Light non-oily feel, Good playDisappears, no silky cream anisette watery, no tack time residual feel,no odor drag, silky feel, good cascade effect 4-D Nice white LightLiquefies on finger on Good play Smooth, not heavy, silky cream anisettepick up; whitening time nice feel odor effect; minor tack 4-E NoticeablyLittle odor Heavy feel, whitening Rubs in Heavy feel, quickly moreeffect quickly becomes significant satin/whipped drag, unpleasant creamwaxy feel with than silky flaking 4-F Grainy Very Rub in gives heavyVery slow Thicker film and (fine- Slight feel with lots of tack, to rubin slow dry down grained); Odor (just doesn't change much gives greasy,heavy good peak what is over rub feel lots of drag present fromemulsifiers)

Example 5

Test Procedure:

The efficacy of topical formulations in recovery of skin barrier wasevaluated. The protocol involved test sites on the volar surface of theforearm. Each test material was tested on at least 25 subjects. Allsubjects had an untreated site. Each test site was 5 cm wide×5 cm long.TEWL readings were taken at each site. The sites were then damaged bytape stripping (using Blenderm™ surgical tape (from 3M Company)) untilTEWL readings were at least 20 mg/m²/h. Just prior to productapplication, baseline TEWL readings were taken. Baseline Skicon andCorneometer readings were also taken at this time. TEWL was measuredwith a Dermalab Evaporimeter (Cortex Technology, Denmark). Skinhydration was assessed by conductance measurement with the Skicon-200(I.B.S., Japan) and MT8C probe (Measurement Technologies, Cincinnati,Ohio) and by capacitance measurement with a Corneometer 820(Courage+Khazaka, Germany). Test material was applied at a dose of 2μl/cm² (50 μl) or 2 μg/cm² (0.05 g) as appropriate to the site. Subjecthad a minimum of 30 minutes acclimation prior to any instrumentreadings. Subjects were in a climate-controlled room. TEWL readings weretaken 30 minutes, 1-hour and 4-hours post application. Final Skicon andCorneometer readings were taken at 4-hours post application.

Formulations Tested:

Petrolatum-Like Compositions:

Example 5-1

2% wt. vegetable wax; 8% wt. HMSBO, and 90% wt. SBO

Example 5-2

6% wt. vegetable wax, 26% wt. HMSBO, and 71% wt.

SBO

Petrolatum: Crompton White Fonoline USP Petrolatum

Soybean Oil: Cargill refined, bleached, and deodorized soybean oil

Mineral Oil: Mineral Oil USP (Heavy)

CORNEOMTER TESTING: After four hours of treatment following skin damage,Example 5-1 provided significant increase in skin moisture content frombaseline, enhanced moisture relative to untreated skin, and exhibitedresults similar to a commercial petrolatum. The skin feel with EXAMPLE5-1 was non-greasy. The Corneometer results are reported in TABLE 6.

TABLE 6 4 hour Corneometer (Mean Change from SAMPLE Baseline) EXAMPLE5-1 8.52 Petrolatum 8.50 Untreated 5.81

SKICON TESTING: EXAMPLE 5-1 provided a significant increase in skinhydration from the baseline, enhanced hydration relative to untreatedskin, and exhibited better hydration than soybean oil. The Skiconresults are reported in TABLE 7.

TABLE 7 4 hour Skicon (Mean Change from SAMPLE Baseline) EXAMPLE 5-1148.77 Petrolatum 394.85 Untreated 99.22 Soybean Oil 83.66

TEWL TESTING: EXAMPLE 5-2 provided a significant decrease in moistureloss from baseline, exhibited better TEWL properties than untreated andsoybean oil, and can be a natural-based alternative to mineral oil forTEWL benefits. The TEWL results are reported in TABLE 8.

TABLE 8 4 hour TEWL (Mean Change from SAMPLE Baseline) EXAMPLE 5-2−13.74 Petrolatum −18.12 Untreated −5.78 Soybean Oil −8.76 Mineral Oil−12.80

EXAMPLES 5-1 and 5-2 provided significant hydration properties to skinfrom baseline, enhanced moisture level relative to untreated skin,provided significant improvement in skin barrier resulting in benefitsin formulations preventing barrier disruption.

Example 6

Lipsticks were formulated using certain petrolatum-like compositions ofthe invention.

The lipstick formulations are provided in TABLE 9.

Ingredient List:

62A: HMSBO (hydrogenated self-metathesized soybean oil)

62D: 20% HMSBO in 300 oil (300 oil is partially hydrogenated, cooled,filtered soybean oil)

62E: 33% HMSBO/67% hydrogenated soybean oil

91A: MSBO (self-metathesized soybean oil)

TABLE 9 INGREDIENTS 9-1 9-2 9-3 9-4 9-5 9-6 9-7 9-8 White Beeswax 8.008.00 8.00 8.00 8.00 8.00 0.00 8.00 Candelilla Wax Regular 5.00 5.00 5.000.00 0.00 5.00 5.00 0.00 Carnauba Wax #1 6.00 6.00 6.00 0.00 0.00 6.006.00 0.00 Softisan 649 7.50 7.50 7.50 7.50 7.50 7.50 7.50 7.50 Uvinul MC80 3.25 3.25 3.25 3.25 3.25 3.25 3.25 3.25 Liponate GC 10.00 10.00 10.0010.00 10.00 10.00 10.00 10.00 Lanolin Oil 0.00 0.00 0.00 10.00 10.000.00 10.00 10.00 Naturechem GTR 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50Floraesters 15 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Jarchol 120 5.005.00 5.00 5.00 5.00 5.00 5.00 5.00 Macadamia Nut Oil 2.50 2.50 2.50 2.502.50 2.50 2.50 2.50 Propyl Paraben 0.20 0.20 0.20 0.20 0.20 0.20 0.200.20 BHT 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Lipovol CO 33.00 33.0033.00 22.00 22.00 0.00 15.00 22.00 62A 0.00 10.00 0.00 22.00 0.00 0.0026.00 0.00 62D 0.00 0.00 10.00 0.00 0.00 0.00 0.00 0.00 62E 0.00 0.000.00 0.00 0.00 0.00 0.00 22.00 91A 10.00 0.00 0.00 0.00 0.00 43.00 0.000.00 Soy Wax 0.00 0.00 0.00 0.00 22.00 0.00 0.00 0.00 OBSERVATIONS GOODTOO HARD GOOD TOO TOO GOOD TOO GOOD SOFT HARD HARD

The above results demonstrate that metathesized soybean oil andhydrogenated metathesized soybean oil can replace several commoningredients utilized in the formulating of lipsticks such as lanolin,carnauba wax, candelilla wax, and castor oil. Hydrogenated soybean oilalone (soy wax) cannot achieve this.

All publications and patents mentioned herein are hereby incorporated byreference. The publications and patents disclosed herein are providedsolely for their disclosure. Nothing herein is to be construed as anadmission that the inventors are not entitled to antedate anypublication and/or patent, including any publication and/or patent citedherein.

Other embodiments of this invention will be apparent to those skilled inthe art upon consideration of this specification or from practice of theinvention disclosed herein. Various omissions, modifications, andchanges to the principles and embodiments described herein may be madeby one skilled in the art without departing from the true scope andspirit of the invention which is indicated by the following claims.

1-83. (canceled)
 84. An emulsion comprising a dispersed phase and acontinuous phase, wherein the dispersed phase comprises an unsaturatedpolyol ester composition, which comprises metathesis oligomers ofunsaturated esters of glycerol and one or more stabilizers; wherein atleast 30 percent by weight of the unsaturated esters of glycerol in theunsaturated polyol ester composition are metathesis oligomers havingfour or more unit oligomers; and wherein no more than 25 percent byweight of the unsaturated esters of glycerol in the unsaturated polyolester composition are metathesis dimers.
 85. The emulsion of claim 84,wherein the emulsion is an oil-in-water emulsion.
 86. The emulsion ofclaim 84, wherein at least 40 percent by weight of the unsaturatedesters of glycerol in the unsaturated polyol ester composition aremetathesis oligomers having four or more unit oligomers.
 87. Theemulsion of claim 84, wherein no more than 60 percent by weight of theunsaturated esters of glycerol in the unsaturated polyol estercomposition are metathesis oligomers having four or more unit oligomers.88. The emulsion of claim 84, wherein no more than 50 percent by weightof the unsaturated esters of glycerol in the unsaturated polyol estercomposition are metathesis oligomers having four or more unit oligomers.89. The emulsion of claim 84, wherein at least 5 percent by weight ofthe unsaturated esters of glycerol in the unsaturated polyol estercomposition are metathesis dimers.
 90. The emulsion of claim 84, whereinat least 15 percent by weight of the unsaturated esters of glycerol inthe unsaturated polyol ester composition are metathesis dimers.
 91. Theemulsion of claim 87, wherein at least 5 percent by weight of theunsaturated esters of glycerol in the unsaturated polyol estercomposition are metathesis dimers.
 92. The emulsion of claim 87, whereinat least 15 percent by weight of the unsaturated esters of glycerol inthe unsaturated polyol ester composition are metathesis dimers.
 93. Theemulsion of claim 84, wherein the metathesis oligomers have an iodinevalue (IV) of 100 or less.
 94. The emulsion of claim 87, wherein themetathesis oligomers have an iodine value (IV) of 100 or less.
 95. Theemulsion of claim 89, wherein the metathesis oligomers have an iodinevalue (IV) of 100 or less.
 96. The emulsion of claim 91, wherein themetathesis oligomers have an iodine value (IV) of 100 or less.
 97. Theemulsion of claim 84, wherein the unsaturated polyol ester compositionhas an iodine value (IV) that ranges from 5 to
 100. 98. The emulsion ofclaim 87, wherein the unsaturated polyol ester composition has an iodinevalue (IV) that ranges from 5 to
 100. 99. The emulsion of claim 84,wherein the one or more stabilizers comprise antioxidants, emulsifiers,or combinations thereof.